Abstract
Abstract The reaction rate of [(PPh3)(MeCN)Ru(µ2-η5:η5-C10H8)(µ-MeSSMe)Ru(MeCN)(PPh3)](BF4)2 (2A), the intermediate of oxidative addition of disulfide to produce bis(thiolato)-bridged complex [(PPh3)Ru(µ2-η5:η5-C10H8)(µ2-SMe)2Ru(PPh3)](BF4)2 (2), changed depending on the solvent (CDCl3, CD2Cl2, CD3COCD3, and CD3NO2). The dependency is well explained by the stabilization energy of solvation of eliminated nitrile during the reaction. The corresponding PhCN complexes [(PhCN)2(PPh3)Ru(µ2-η5:η5-C10H8)Ru(PPh3)(PhCN)2](BF4)2 (1C) and [(PPh3)(PhCN)Ru(µ2-η5:η5-C10H8)(µ-MeSSMe)Ru(PhCN)(PPh3)](BF4)2 (2C) were newly synthesized to know the effect of nitrile. The intermediate of oxidative addition of diselenide [(PPh3)(MeCN)Ru(µ2-η5:η5-C10H8)(µ-MeSeSeMe)Ru(MeCN)(PPh3)](BF4)2 (3A) and the corresponding end product [(PPh3)Ru(µ2-η5:η5-C10H8)(µ2-SeMe)2Ru(PPh3)](BF4)2 (3) were also isolated, and the structures were determined by single-crystal X-ray structural analysis.
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